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Patented July 5, 1932 I UHTED STA assaxzs PATENT OFFICE- CHARLES J. STROSACKEB AND WILBUR '1. STEPHENSON, OF MIDLAND, MICHIGAN, AS- SIGN OBS TO THE DOW CHEMICAL COMPANY, OF MIDLAND, MICHIGAN, A CORPORA- TION OF MICHIGAN CONTINUOUS METHOD O1 MAKING ALKALI-METAL ACETATES Application filed December 5, 1929. Serial No. 411,976.

This invention'has regard to methods for preparing an alkali metal acetate by reacting an alkali metal hydroxide and acetylene in the presence of water. The reaction is represented by the equation:

wherein M is an alkali metal, e. g. sodium or potassium. In a prior application Ser. No. 323,199, filed Dec. 1, 1928, a method of the above general character has been disclosed wherein a closed reactor is charged with a solid alkali metal hydroxide, e. g. sodium hydroxide, in comminuted form and heated to a temperature preferably between 200 and 300 C. Thereupon acetylene and water are introduced until a gas pressure of about pounds per square inch is built up, the supplies then being shut off and the mixture of solids and gases allowed to react, with suitable stirring to expose fresh solid surfaces, until a sample ofv the gas upon testing is found to be substantially free from acetylene. Then the waste gas, consisting chief-' ly of hydrogen with a little water vapor, is vented, a fresh charge of acetylene and water introduced, and the operation repeated. Proceeding in this way with alternate charging and reacting periods a yield of acetate in excess of 90 per cent, based upon either the acetylene or alkali employed, may be obtained.

Such mode of operation, however, is subject to certain disadvantages, particularly when applied in large scale commercial apparatus. For example, we have found that a uniform reaction rate is not maintained throughout the duration of the entire reaction. The initial reaction starts slowly and reluctantly, then proceeds very rapidly over a considerable period, at times with almost instantaneous absorption of the acety lene, and finally diminishes gradually in speed until the time required to react a single charge of acetylene becomes excessively long.

During-the intermediate. period, when optimum conditions prevail, the heat of reaction developed is sufficient to maintain an ;o approximately uniform reaction temperature, but with the intermittent mode of operation described in the aforesaid application the temperature fluctuates greatly and other irregularities are encountered which at times greatly interfere with the proper control of the process, while frequently heat from an outside source must be provided for maintaining the apparatus with its charge at the desired temperature.

7 Another unfavorable circumstance is that only a relatively small weight of acetylene can be introduced into the closed reaction chamber at one time. Experience has shown that at the beginning of. the reaction there are approximately 150 molecular equivalents of alkali metal hydroxide present in a usual charge to one equivalent of acetylene. In order to'procure the reaction of the major portion of such hydroxide, therefore, it is necessary to introduce in the neighborhood of 150 separate charges of acetylene, thus involving considerable loss of time from frequent stopping and starting of apparatus, and also an unduly large amount of handling and supervision of the apparatus.

Still another disadvantage is the danger of explosion, when working with acetylene under pressure. The safe upper limit of pressure in the present process, when a rich acetylene gas is used, lies. between 50 and pounds per square inch, and in order to employ such pressures without risk of occasional slight explosions accompanied by decomposition of materials it is necessary to maintain about one atmosphere steam pressure in the reactor at all times.

For the foregoing reasons, it becomes desirable to devise an improved mode of operation whereby the process may be conducted continuously over considerable periods of time at a fairly uniform temperature and at about atmospheric pressure. The invention, accordingly, consists in the steps hereinafter fully described and particularly pointed out in the claims, the annexed drawing and following description setting forth but a few of the various Ways in which the principle of the invention may be used.

In said annexed drawing, the single figure is a flow sheet illustrating one mode of procedure for carryin out the invention.

We have found t at, although the reaction in accordance with the Equation S11) is some- I what slow to start when the a ali metal hydroxide is the sole solid present, as soon as a small amount of acetate has been formed of the amount of alkali in the original charge has been reacted. In other words, so long as the solids contain at least 1 mole unreacted alkali metal h droxide to 2 moles alkali metal acetate t e reaction rate will not be retarded to any material extent. B adding fresh alkali metal hydroxide, eit er continuously .or at intervals, to the reaction mixture so as to maintain a molecular ratio of hydroxide to acetate approximately equal to, or somewhat in excess of, 1 to 2 and dischargin an equivalent amountmof reacted materia, it is feasible to institute a continuously operating procedure under optimum conditions, thus efiecting considerable savings in labor and handling of materials and greatly increasing the output for a given size of ap aratus. Under such improved proceduret eprocess may be rendered almost entirely self-sustaining thermally, inasmuch as the heat of reaction, as aforesaid, is suflicient to maintain the requisite temperature steadily while the optimum reaction rate continues in effect.

Such modified form of procedure involves working up a reaction product containing ap roximately 1 mole caustic alkali to '2 mo es alkali metal acetate and separating the two com unds-from each other. This can be satis actorily accomplished by dissolving the reaction mixture in water to form asolution of suitable concentration and crystallizing out the acetate, leavin the al- I! kali metal hydroxide in solution. highly pure acetate product may be prepared in this way, while the residua solution may be evaporated to recover the alkali metal hydroxide, which is returned to the process. I We have further found that the amount of water present, either as vapor or absorbed by the solid reactants, and the manner of introducing the same, have an important in fluence upon the course of the reaction. As already set forth in the prior application referred to above, it is essential that the amounts of water present at any time shall be insufiicient to cause fusion or liquefaction of the reaction mixture. Dn the other hand,

u a deficiency of water may lead to more or less decomposition of the product, according tothe equation:

2 oH.oooM+uon=M.oo.+oH,

perature and the com osition o the mixture of alkali metal hydrox de and acetate actually present. Ingeneral,thehighertheacetatecontent the ater the excess of water that can be absor ed without tending to liquefy the mixture, but in any case it is inadvisable to have more than about percent excess of water over acetylene in the reaction zone.

The water may be introduced in various wa s, as steam or as an aqueous alkali metal hy roxide solution. A particularly advantageous manner of adding the water, which is adapted to a continuous mode of operation, consists in saturating the acetylene with water vapor by bubbling the gas through .water and then passing the mixture of gas and vapor into the reactor. This permits an easy regulationof the relative amounts of 95 acetylene and water that are admitted to the reaction by controlling the temperature of the water through which the gas is bubbled. Since the vapor tension of water is very nearly equal to one half normal atmospheric ressur'e at a temperature of 815 (3., it

ollows that, b maintaining the water through which t e acetylene is bubbled at such temperature, the issuing mixture of gas and vapor will contain substantially equal volumes, or equal moles, of each; that is, the theoretical combining proportions called for according to Equation (1). A slight deviation from the temperature given, or fluctuations of temperature within a few degrees either way, will not alter the proportions of acetylene and water vapor sufiiciently to afiect "the reaction materially. Likewise, temperature adjustment may be made according to the existing barometric pressure, while by increasing the water temperature an excess of water vapor may be provided for the'reaction, if so desired.

For carrying out our improved method or process We may proceed, for example, in the manner described below, but it is understood that the detailed procedure there iven is presented for the purpose of illustration and that the invention shall not be limited t ere: by except as hereinafter specifically provided 3 in the claims. The sequence of steps therein will appear upon referring to the flow sheet.

A stationary horizontal cylindrical reactor of iron or steel, provided with suitable stirring means, is charged about one half full ysis of such material is:

The temperature of the charge is raised to 1 approximately 280 to 290 C. b means of external heating. A quantit 0 about 200 pounds of commercial flake so ium hydroxide is then added, the solids being kept actively in motion by means of the stirrer, and through a suitable inlet at one end of the reactor a mixture of approximately equal parts by volume of acetylene and water vapor is admitted, such mixture having been conveniently prepared by bubbling acetylene 20 as through a body of water at a temperature etween 80 and 85 C. as already described. The rate of introduction of the acetylenewater vapor mixture is regulated so that the heat of reaction maintains the temperature within the reactor between about 250 and 290 C. From this oint, then, the recess is thermally self-su cient and no urther heat from an external source is required. The exit gases issuing from the outlettherefor provided at the opposite end of the reactor consist of 95 per cent ormore hydrogen, figured on a dry basis. Additional quantities of about 50 pounds each of flake sodium hydroxide are charged in at intervals of about 85 minutes until the space within the reactor is about two thirds filled. Thereafter the flow of gas is continued until an analysis of a sample of the charge shows that the NaOH content thereof has fallen to about per cent. Then a quantity of about 1000 pounds of reaction product is discharged throu h a suitable outlet provided therefor wit out necessarily interrupting the flow of gas, after which the regular addition of sodium hydroxide is resumed and operation continued as before. The material discharged from the reactor in ,a more or less pulverulent form is allowed to cool, and then dissolvedin suflicient water to form a solution that is saturated with respect to the hydrated sodium acetate, CH COONa3l-I O, at a temperature between about and C. A representative anal- 5 g :Per cent CH COONa 72.5 NaOH 20.2 Na CO 4.4 NaCl 1.4

A solution thereof saturated with hydrated sodium acetate at 60 G. contains approximately 51 per cent anhydus solids and 4.8 per cent water. The solution is warmed to, say, C. and treated with lime to causof iron compounds. The clear filtrate is then ticize most of the carbonate content thereof, and then filtered hot to remove the precipitated CaGO, and other insolubles, e. g. iron hydrate, in case the material contains traces 7o cooled to crystallize out hydrated sodium acetate. The latter operation may conveniently be carried out in two stages, first cooling'by natural means to about room tem erature to produce a first crop of crystals, w ich 75 are separated, and then cooling with artificial refrigeration to about 0 C. to produce a further crop of crystals. The crystals are washed with water and purified from traces of NaOH by recrystallizmg from water solution. By t is means as much as 96 per cent of the acetate may be separated as crystals of composition CH3COONa.3H O, leaving a mother liquor containing substantially all of the sodium h droxide together with the small remainder o the acetate. The mother liquor ma be evaporated to remove water, solidifie and flaked without decomposing the acetate contained therein, and the recovered product may then be returned to the process. It is also possible to se arate the acetate from the reaction product y crystallizing as the anhydrous salt from more concentrated solutions than those just referred to, but the latter method is less desirable owing to the form of the anhydrous crystals as usually obtained which are diflicult to filter and wash clean. The method of procedure just described in detail maybe defined as being semi-continuous in character. Iii other words the feeding of solid materials and the discharging of solid product is intermittent, whereas the introduction and discharge of gaseous materials and products is for all practical puroses continuous, and most of the advantages inherent in continuous operation are realized. However, the method is easily capable of being adapted to a fully continuous mode of operation by provision for a continuous feed of flake or powdered sodium hydroxide, and for a continuous discharge of solid product.

The reaction proceeds with ra id conversion of materials to acetate pro uct within the temperature range of 250 to 290 C. specified in the detailed example. However by suitably adjusting the rates of supply oi gas and alkali metal hydroxide, a good conversion may be achieved at temperatures as low as 200 C. Temperatures higher than 290, e. g. up to about 300 C. or somewhat higher may also be employed, but at the risk of reaching orexceeding' the fusion point of the solid mixture of sodium h droxide and acetate, and decomposition o acetate product also commences at temperatures between 300 and 325 C. In general, therefore, a satisfactory tem erature range is between 200 and 300 with a preferred range of about 250 to 290 C. 3%

T The 'com tion of the solid reaction mixture is pre erably to be controlled so that the ratio by wei ht of N aOH to CILCOONa is between the imits of Hand 3%, corresponding approximately to a molecular ratio of from to 1} Within such limits the mixture remains sensibly dry at all times with the usual control of temperature and of water introduced. When the proportion of NaOH is increased it becomes more difiicult to prevent fusion-of the mixture, while if the content of N aOH falls much below the limit stated the reaction rate-is diminished and.

' When such diluted mixtures are reacted it may be advantageous to employ moderate pressure in order to maintain about the same concentration of acetylene in the reaction chamber as above without materially increasing the gas velocity, which may safely be done under such condition without introducing any risk of explosion. Otherwise no essential modification of the procedure already described would be called for.

Apparatus details mentioned in the descriptlon do not imply an limitation upon the type or form thereo or materials of construction therefor, which may be employed in carrying out the invention. Other forms of apparatus, e. g. a revolving reactor "equipped with any suitable means for stirring 'in comminuted form at a temperature above 200 (3., but below that at which decomposition of acetate occurs, continuously introducing acetylene and water vapbr thereto, while stirring thesame, discharging reacted solid roduct and separating alkali metal acetate rom unreacted hydroxide therein.

2. The method of making an alkali metal a rich acetylene gas, the reaction is.

a'seaaae acetate which comprises providing a re I in comminuted form at a temperature above 200 0., but below that at which decomposition of acetate occurs, continuously introducing acetylene and water vapor thereto, while stirring the same, discharging reacted solid product, dissolving such product in water, crystallizing alkali metal acetate from the solution, separating the crystals, dehydrating the residual mother liquor containing alkali metal hydroxide together with a small amount of acetate and returning such dehydrated material to the principal reaction.

4. The method of making an alkali metal acetate which comprises providing a sensihlv dry mixture of the corresponding hydroxide and acetate in comminuted form, and at a temperature between 200 and 300 (1, continuously introducing acetylene and water vapor in aproximately equimolecular proportion thereto, while stirring the same. maintaining a molecular ratio of alkali metal hydroxide to acetate in the reaction mixture between about and 1} byrfurther additions of such hydr oxide, discharging reacted solid product and recovering the acetate from the product.

5. The method of making an alkali metal acetate which comprises providing a sensibly dry mixture of the corresponding hydroxide and acetate in comminuted form, and at a temperature between 200 and 300 6., continuously introducing acetylene and water vapor in approximately equimolecuiar proportion thereto, and at such rate that the temperature of the mixture is maintained between the limits stated', while stirring the same. maintaining a molecular ratio of alkali metal hydroxide to acetate in the reaction mixture between about ther additions of such hydroxide, discharging reacted solid product, dissolving such product in water and crystallizing the acetate from the solution.

6. The method of making an alkali metal acetate which comprisesproviding a sensibly dry mixture of the corresponding hydromde and acetate in comminuted form, and at a temperature between 200 and 300 G, continuously introducing acetylene and water vapor in approximately eqnimolecular propintion thereto, and at such rate that the temperature of the mixture is maintained beand i by furtween the limits stated, while stirring the same, maintaining a molecular ratio of alkali metal hydroxide to acetate in the reaction mixture between about and by further additions of such hydroxide, discharging reacted solid product, dissolving such product in water, crystallizing the acetate from the solution, separating the crystals, dehydrating the residual mother liquor containing alkali metal hydroxide together with a small amount of acetate and returning such dehydrated material to the principal reaction.

7. The method of making sodium acetate which comprises providing a sensibly dry mixture of sodium hydroxide and sodium acetate in comminuted form and at a temperature above 250 C. but below that at which decomposition of the acetate occurs, continuously introducing acetylene and water vapor in approximately equimolecular proportion thereto and at such rate that the temperature of the mixture is maintained between the limits stated, while stirring the same, maintaininga molecular ratio of sodium hydroxide to acetate in the reaction mixture between about and 1; by further addition of such hydroxide, discharging reacted solid product and recovering sodium acetate from p the product.

8. The method of making sodium acetate which comprises providing a sensibly dry mixture of sodium hydroxide and sodium acetate in comminuted form and at a temperature above 250 C. but below that at which decompositionv of the acetate occurs, continuously introducing acetylene and water vapor in approximately equimolecular proportion thereto and at such rate that the temperature of the mixture is maintained between the limits stated, while stirring the same, maintaining a molecular ratio of sodium hydroxide to acetate in the reaction mixture between about and 1} by further addition of such hydroxide, discharging reacted solid product, dissolvingsuch product in water and crystallizing sodium acetate as CH COONa.3H O from the solution.

9. The method of making sodium acetate which comprises providing a sensibly dry mixture of sodium hydroxide and sodium acetate in comminuted form and at a temperature above 250 C. but below that at which decomposition of the acetate occurs,

continuously introducing acetylene and water vapor in approximately equimolecular proportion thereto and at such rate that the temperature of the mixture is maintained between the limits stated, while stirring the same, maintaining a molecular ratio of sodium hydroxide to acetate in the reaction mixture between about and by further addition of such ydroxide, discharging reacted solid product, dissolving such product 'in water, crystallizing sodium acetate as method of recovering the acetate from such mixed product which comprises dissolving the same in water, crystallizing a substantial portion of the acetate from the solution as CI-LCOONafiI-LO, separating the crystals and returning the hydroxide and residual acetate in the mother liquor to the principal reaction.

11. In the manufacture of sodium acetate by reacting sodium hydroxide with acetylene and water at a temperature between about- 200 and about 300 C. to produce a mixture of said acetate and unreacted hydroxide, the method of recovering the acetate from such mixed product which comprises dissolving the same in water, crystallizinga substantial ortion of the acetate from the solution as CH COONa3H O, separatingthe crystals, dehydrating the mother liquor containing sodium hydroxide and the residual acetate 7 and returning such dehydrated mixture of the principal reaction. 1 Sggned by us this 29th day of November,

' CHARLES J. STROSA'GKER. WILBUR T. STEPHENSON. 

